Perinones

ABSTRACT

10,22-DIOXODIBENZIMIDAZO (1, 2-B : 1&#39;&#39;, 2&#39;&#39;-B&#39;&#39;) DIBENZO (DE: D&#39;&#39; E&#39;&#39;)-P-DIOXINO (2, 3-G : 5, 6-G&#39;&#39;) DIISOQUINOLINES AND ISOMERS ARE PREPARED, BEING USEFUL AS LUMINESCENT MATERIALS OR PHOSPHORS.

United States Patent Primary Examiner-Donald G. Daus Anomey- Frank R.Ortolani ABSTRACT: 10,22-dioxodibenzimidazo (l, 2-b l, 2-b') dibenzo(de: d e)-p-dioxino (2, 3-g 5, 6-g') diisoquinolines and isomers areprepared, being useful as luminescent materials or phosphors.

Inventor Edward E. Jafie Union, NJ. Appl. No. 795,506 Filed Jan. 31,1969 Patented Nov. 23, 1971 Assignee E. I. du Pont de Nemours andCompany Wilmington, Del.

BERINONES 2 Claims, 2 Drawing Figs.

[1.8. CI. 260/282, 106/288, 252/301.2 R, 260/346.3, 260/578, 313/109Int. Cl. C07d 57/02 0 PAIENTEDunv 23 197i IG.Z

mvsm"on EDWARD E. JAFFE flmfi 200 FlG.l

ATTORNEY TEMPERATURE PERINONILS This invention relates to organicphosphors which are excited by long wavelength ultraviolet light andrespond with a bright red emission.

The luminescent materials commonly used as thin layers on the inside offluorescent lamps, high-pressure mercury vapor lamps and sign tubingsare generally referred to as fluorescent powders or phosphors. These areinvariably inorganic in nature, and some of the best and most widelypublicized are expensive. Under the circumstances, the possibility ofutilizing organic compounds for similar purposes should be considered.Heretofore there has been no organic candidate which showed sufficientresponse under the conditions of use to render it of interest.

STATEMENT OF THE INVENTION The present invention provides noveldiperinone compounds represented by the following structural formulas:

and

of is l0.22-diox- The compound The compounds of this invention exhibitfluorescence when excited by 2537A. radiation; the exciting radiation inthe usual fluorescent lamps, and by the 3660A. radiation whichconstitutes an appreciable proportion of the emission within mercuryvapor lamps. The'outstanding response of these new phosphors toexcitation with 3660A. radiation, and the reddish color of the emittedlight-desirable for "correcting" the color of mercury lamps-make theseproducts of particular value for use as a component part of mercuryvapor lamps. The phosphors also are useful in pigment form. Other usefulapplications of the discovery will occur to the artisan.

In the drawings:

FIG. lshows the fluorescent spectrum for a diperinone compound of theinvention, having thereon a prior art spectrum for comparison purposes.The wave length of fluorescent emission is plotted against arbitraryintensity units, the spectrum indicated as A being that of a diperinoneof this invention, and B being that for one of the best currentlyavailable red phosphors.

FIG. 2 shows a graph on which intensity of fluorescent emission inarbitrary units is plotted against temperature.

These new diperinone compounds of this invention are prepared bychemical techniques presently known to the artisan. Of the synthesesavailable, a preferred route is. schematically, as follows:

l. Naphthalic anhydride is sulfonated according to the method of Anselmand Zuckmayer (Ber. 32. 3283 1899)):

o o .0 0 0T 0 2. The 3-sulfonuphthalic anhydride thus prepared isconverted to 3-hydroxynaphthalic anhydride by the method of ZollingerHelv. Chim. Acta 33,530 l950)):

3. The resulting anhydride product is then brominated by the method ofDziewonslti et al. (CA. 26. 5942( l932)):

4. The brominated product is condensed with o-phenylenediamine toperinone:

5. In the final reaction the diperinone derivative is prepared by anintermolecular; dehydrobromination of 2 mols of the perinone, therebyforming a compound of this invention, that is, one of compounds 1, II,and III hereinbefore identified.

The invention will be further described with the following specificexample, in ,which the details are given by way of illus-. tration andnot by way of limitation.

EXAMPLE A mixture of 2.93 parts (0.0l mols) of3-hydroxy-4-bromonaphthalic anhydride, 1.08 parts (0.0l mols) ofo-phenylene diamine and 210 parts of acetic acid is heated to reflux,and refluxing is continued for hours. During the refluxing a heavyyellow precipitate forms, which increases in amount as the refluxingproceeds. This product is isolated by filtration, and is washed withwater until free of acid and finally dried. Yield is 3.2 parts (i.e.87.7 percent of theoretical, assuming a product corresponding to thecomposition C l-l BrN O The melting point of a small sample of thehydroxybromoperinone crystallized from a large amount of hot acetic acidis 328 to 340 C., probably indicating a mixture of the compounds asshown in formulas Iv and V.

Analysis C. 59.20. H. 2.47; N. 7.67

Calculated for C ,,H.,BrN,O,:

. 4 C. 59.10; H. 2.84; N. 7.36

Found:

'A mixture of one part of the hydroxybromoperinone, one part ofanhydrous potassium carbonate and 60 parts of dry nitrobenzene is heatedto reflux and maintained at reflux temperature for 5 hours. During thisoperation any water which forms is permitted to escape from the reactionmixture. The

' hot mixture is filtered and the filter cake washed thoroughly withnitrobenzene, then successively with alcohol, water and again withalcohol. The yield of productis 0.23 parts (35.8 percent of theory,assuming a molecular weight of C H N. 0.). (In another example carriedout in essentially the same manner, a yield of 50.2 percent is;obtained.) In still another experiment wherein some cupric acetate isincluded in the hydroxybromoperinone reaction mixture. the yield ofproduct is about 36 percent.

The product is purified by recrystallization from acid as follows:Asolution of 2.63 parts of the pulverized dry product in 18.4 parts ofl00'pe rce n,t sulfuric acid is prepared by stirring at a temperaturenot above C. After solution is complete, as judged by microscopicexamination of a sample, the acid concentration is gradually lowered to90 percent by dropwise addition of water, the rate being such as tomaintain the temperature of the mixture below 10 C. throughout. Themixture is stirred for an additional hour at 10 C., and the precipitatedsulfate of the desired product is filtered and thoroughly washed with 80percent sulfuric acid. The sulfate filter cake is then hydrolyzed withice and water, and the resulting diperinone compound isolated byfiltration and washing free of acid to give 1.01 parts of red shadeyellow solid. For analytical purposes 1.26 parts of the product isextracted twice with 450 parts of nitrobenzene and once with 570 partsof boiling N,N-dimethyl formamide. The purified sample does not meltup.to"4'00 C.

Analysis 7 Calculated forCgfluNiorz C, 76.00; H. 2.82; N, 9.86 Found: C.75.04; H. 2.80; N. 9.95

A diperinone product prepared according to the general procedure of theexample has been examined and tested. FIG. I shows a comparison of thefluorescent emission spectrum (A) of the product obtained with one ofthebestcurrently available red phosphors'(y Eu,, VOl). (B) underexcitation by relatively long ultraviolet radiation(3660A). Intensitiesare on a qualitative scale. Visual observation confirms the appreciablygreater brightness of the product of this invention. It is concludedthat such strong, deep red emission under excitation at 3660A. wouldrender the product of this invention superior as a color-correctingphosphor when used for this purpose, for example on the inner surface ofthe outer envelope of high-pressure mercury vapor lamps, whereby thevisual appearance of the resulting light would be changed from blue toyellowish while at the same time increasing the lumen output. FIG. 11shows the relative intensity of the fluorescent emission spectrum of theproduct at temperatures up to 300 C. It will be noted that even thoughthe intensity decreases by approximately 40 percent at 300 C. bycomparison with that at C. as shown in FIG. 11 where the intensity ofemission in arbitrary units is plotted versus temperature, it is stillhigher than that of Y Eu VO See FIG. 1, assuming that the emissionintensity ofthe latter were constant throughout this temperature range.Consequently, the product of this invention would be expected to be asuperior red phosphor for color-correction of discharge devices excitedby light of 3660A. even at the higher temperature.

The product of this invention is a red-shade yellow material which isextremely insoluble in common organic solvents. When dispersed in anorganic. vehicle, for example lithographic varnish, and drawn down on asupport, it is a redshade yellow pigment which luminesces strongly uponstimulation by ultraviolet radiation. After exposure for 72 hours somedarkening occurs, but most of the luminescence is still retained. Evenafter dilution of the dispersion with ZnO (1:100) some luminescence isobserved on shining ultraviolet light on the extended dispersion.

While the invention has been described above with certain detail, itshould be understood that changes can be made by the artisan. Forexample, in preparing diperinones other solvents, temperatures ofreaction. and methods of purification. may be used in place of thecorresponding condition set forth in the example. Also, although theperinone was made by condensation with o-phenylene diamine, it isobvious that the reaction is also applicable to condensation with otherorthoor peridiamines. These would include 1,2- diaminonaphthalene,2,3-diaminonaphthalene, l ,8-diaminonaphthalene, etc. These reactants aswell as the aforementioned o-phenylene diamine, may be substituted bysuch groups as lower alkyl. lower alkoxy, halogen, etc. to producecorrespondingly substituted diperinones.

What is claim is:

I. A diperinone compound having one of the structural formulas and 2. Ared shade yellow compound having the structure given in claim 1 whichluminesces upon stimulation by ultraviolet light. I

2. A red shade yellow compound having the structure given in claim 1which luminesces upon stimulation by ultraviolet light.